CN102385266B - Electrophotographic photoconductor and image forming apparatus including same, and coating solution for undercoat layer formation in electrophotographic photoconductor - Google Patents

Abstract

The invention relates to an electrophotographic photoconductor and an image forming apparatus including the same, and a coating solution for undercoat layer formation in the electrophotographic photoconductor. The electrophotographic photoconductor comprises a conductive support, an undercoat layer and a photosensitive layer, the undercoat layer and the photosensitive layer being formed on the conductive support in sequence, wherein the undercoat layer contains a binder resin, titanium oxide particles surface-treated with at least anhydrous silicon dioxide and titanium oxide particles surface-treated with at least hydrous silicon dioxide.

Description

Photoelectric conductor for electronic photography and comprise its image processing system, and the undercoat of photoelectric conductor for electronic photography form and use coating fluid

Technical field

The present invention relates to photoelectric conductor for electronic photography.More specifically, the present invention relates to have the photoelectric conductor for electronic photography of the undercoat (middle layer) between conductive carrier and photographic layer and the undercoat formation coating fluid of image processing system and photoelectric conductor for electronic photography.

Background technology

Usually, using the electrophotographic method of the photoconductor with photoconductivity is a kind of information recording technology of utilizing the photoconductive phenomenon of photoconductor.

According to described method, at first by corona discharge in the dark, utilize electricity to make the surface uniform of photoconductor charged, then implement image exposure, thereby exposed portion is optionally discharged, on unexposed portion, form thus electrostatic image.Subsequently, by electrostatic attraction, painted and charged fine particle (toner) is attached to latent going up mutually and forms visual picture, form thus image.

In these a series of processes, require photoconductor to have following essential characteristic:

1) in the dark can make the photoconductor uniform charged to suitable potential;

2) in the dark, described photoconductor has high electric charge hold facility and electric discharge minimizing;

3) described photoconductor has excellent light sensitivity and the rapid discharge by utilizing light to irradiate.

In addition, require described photoconductor aspect higher stability and permanance, having following feature, for example, can easily the electric charge on photoconductor surface be removed, thereby stay the rest potential of reduction; Described photoconductor has the flexible of physical strength and excellence; When reusing, the electrical characteristics of described photoconductor, particularly charging property, light sensitivity and rest potential can not change; And described photoconductor has tolerance to heat, light, temperature, humidity and ozone degradation.

Because the photoelectric conductor for electronic photography that has been put in the recent period actual use has the photographic layer formed on conductive carrier separately, so be easy to generating source, from the carrier injection of conductive carrier, make surface charge disappear on microcosmic or reduce, thereby producing image deflects.

In order to prevent this image deflects, in order to cover the lip-deep defect of conductive carrier, in order to improve charging property, for the adhesiveness that improves photographic layer and in order to improve coating, undercoat (middle layer) is set between conductive carrier and photographic layer.

Routinely, considered various resin materials and the resin material that contains inorganic compound particles such as titania powder are used as to undercoat.

As with the resin individual layer, forming the material of undercoat, known resin material such as tygon, polypropylene, polystyrene, acrylic resin, vestolit, vinyl acetate resin, urethane resin, epoxy resin, vibrin, melamine resin, silicones, polyvinyl butyral resin and polyamide arranged, comprise the copolymer resin of two or more these repetitives and other casein, gelatin, polyvinyl alcohol (PVA) and ethyl cellulose etc., wherein polyamide particularly preferably.

Yet about individual layer with resin such as polyamide photoelectric conductor for electronic photography as undercoat, rest potential is accumulated in a large number, susceptibility descends and produces the image atomization.Under low-humidity environment, this trend is remarkable especially.

Therefore, in order to prevent producing image deflects and improve rest potential because of conductive carrier, proposed to contain the undercoat (Japanese kokai publication sho 56-52757 communique) of surperficial untreated titania powder, contain the undercoat (Japanese kokai publication sho 59-93453 communique) that utilizes aluminium oxide etc. to be coated with the titania fine particle that improves the titania powder dispersiveness, contain the undercoat (Japanese kokai publication hei 4-172362 communique) that utilizes the surface-treated metal oxide particle of titanate coupling agent and contain the undercoat (Japanese kokai publication hei 4-229872 communique) that utilizes the surface-treated metal oxide particle of silane compound.Yet, when using photoconductor for a long time, can not avoid the impact of environmental change on susceptibility and image.Therefore, expect the photoelectric conductor for electronic photography with the characteristic be further enhanced aspect permanance.

Summary of the invention

The objective of the invention is suppress the deteriorated of the photoconductor susceptibility caused because of temperature and humidity and provide: a kind of photoelectric conductor for electronic photography, described photoelectric conductor for electronic photography are difficult for the susceptibility variation occurring and there is no image deflects and atomization because reusing; The image processing system that comprises described photoelectric conductor for electronic photography; With the undercoat formation coating fluid in described photoelectric conductor for electronic photography.

The present inventor has been found that, when containing, undercoat utilizes the surface-treated TiO 2 particles of anhydride silica and while utilizing two kinds of particles of the surface-treated TiO 2 particles of aqueous silicon dioxide, can improve the dispersiveness in undercoat, can prevent the generation of condensation product, filming can be smooth and have the resistance of even maintenance, and can obtain and be difficult for because of environmental change through affecting adversely and potential property and the picture characteristics of stable photoconductor under various environment.

Particularly, the present inventor has conducted in-depth research and effort, found that, utilization has the photoelectric conductor for electronic photography of following undercoat can realize above-mentioned purpose, described undercoat contains adhesive resin and utilizes the surface-treated TiO 2 particles of anhydride silica and utilize surface-treated two kinds of particles of TiO 2 particles of aqueous silicon dioxide at least, thereby has completed the present invention.

Therefore, according to an aspect of the present invention, a kind of photoelectric conductor for electronic photography that comprises conductive carrier, undercoat and photographic layer is provided, described undercoat and photographic layer are formed on described conductive carrier successively, and wherein said undercoat contains adhesive resin, utilize the surface-treated TiO 2 particles of anhydride silica at least and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide at least.

According to another aspect of the present invention, a kind of photoelectric conductor for electronic photography is provided, wherein with 80/20～30/70 weight ratio, comprises and describedly utilize the surface-treated TiO 2 particles of anhydride silica and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide.

According to another aspect of the present invention, provide a kind of photoelectric conductor for electronic photography, the wherein said surface-treated TiO 2 particles of aqueous silicon dioxide that utilizes is the TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process.

The invention provides a kind of photoelectric conductor for electronic photography, the wherein said surface-treated TiO 2 particles of aqueous silicon dioxide that utilizes is to utilize the aqueous silicon dioxide that mixes with 10/90～90/10 weight ratio and the surface-treated TiO 2 particles of potpourri of aluminium hydroxide.

According to another aspect of the present invention, provide a kind of photoelectric conductor for electronic photography, wherein said photographic layer contains phthalocyanine as charge generating material.

According to another aspect of the present invention, provide a kind of photoelectric conductor for electronic photography, wherein said photographic layer contains and is selected from following phthalocyanine as charge generating material:, τ type metal-free phthalocyanine; In X-ray diffraction spectrum, locate to have the crystal-type TiOPc at maximum diffraction peak at angle, 27.3 ° of Prague (Bragg) (2 θ ± 0.2 °); And in X-ray diffraction spectrum, locate to have diffraction peak at 7.3 °, 9.4 °, 9.7 ° and 27.3 ° of Bragg angles (2 θ ± 0.2 °) at least, wherein at 9.4 ° and 9.7 ° of diffraction peaks of locating both bifurcated peak (branch peaks) and than large 27.3 ° of diffraction peaks of locating clearly, and at 9.4 ° of diffraction peaks of locating crystal-type TiOPc that is maximum diffraction peaks.

According to another aspect of the present invention, provide a kind of photoelectric conductor for electronic photography, wherein said TiO 2 particles has the average primary particle diameter of 20nm～100nm.

According to another aspect of the present invention, a kind of photoelectric conductor for electronic photography is provided, wherein so that 80/20～30/70 weight ratio use is described, utilizes the surface-treated TiO 2 particles of anhydride silica and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide at least, the weight ratio as 10/90～95/5 with respect to described adhesive resin of take in undercoat comprises described TiO 2 particles, and described adhesive resin is polyamide.

According to another aspect of the present invention, a kind of photoelectric conductor for electronic photography is provided, wherein said undercoat has the film thickness of 0.05 μ m～5 μ m, described photographic layer is the multilayer photographic layer that comprises charge generation layer and charge transport layer, and described charge generation layer has the film thickness of 0.05 μ m～5 μ m.

According to another aspect of the present invention, a kind of image processing system that comprises photoelectric conductor for electronic photography is provided, described photoelectric conductor for electronic photography comprises conductive carrier, undercoat and photographic layer, described undercoat and photographic layer are formed on described conductive carrier successively, described undercoat contains adhesive resin, utilizes the surface-treated TiO 2 particles of anhydride silica and utilizes the surface-treated TiO 2 particles of aqueous silicon dioxide at least, and described photographic layer contains and is selected from following phthalocyanine as charge generating material: τ type metal-free phthalocyanine; In X-ray diffraction spectrum, locate to have the crystal-type TiOPc at maximum diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 27.3 °; At least the Bragg angle (2 θ ± 0.2 °) 7.3 °, 9.4 °, 9.7 ° and 27.3 ° locates to have diffraction peak in X-ray diffraction spectrum, wherein at 9.4 ° and 9.7 ° of diffraction peaks of locating bifurcated peak and than large 27.3 ° of diffraction peaks of locating clearly both, and at 9.4 ° of diffraction peaks of locating crystal-type TiOPc that is maximum diffraction peaks.

According to another aspect of the present invention, provide a kind of undercoat for the manufacture of photoelectric conductor for electronic photography to form and use coating fluid, described photoelectric conductor for electronic photography comprises conductive carrier, undercoat and photographic layer, described undercoat and photographic layer are formed on described conductive carrier successively, and described coating fluid contains adhesive resin, utilize the surface-treated TiO 2 particles of anhydride silica at least and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide at least.

According to another aspect of the present invention, provide a kind of coating fluid, its weight ratio with 80/20～30/70 comprises describedly to be utilized the surface-treated TiO 2 particles of anhydride silica and utilizes the surface-treated TiO 2 particles of aqueous silicon dioxide.

According to another aspect of the present invention, provide a kind of coating fluid, the wherein said surface-treated TiO 2 particles of aqueous silicon dioxide that utilizes comprises the TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process.

The present invention also provides a kind of coating fluid, and the wherein said surface-treated TiO 2 particles of aqueous silicon dioxide that utilizes is to utilize the aqueous silicon dioxide that mixes with 10/90～90/10 weight ratio and the surface-treated TiO 2 particles of potpourri of aluminium hydroxide.

Photoelectric conductor for electronic photography of the present invention can suppress the fluctuation of photoconductor microscopic characteristics, particularly susceptibility and rest potential, and prevents the generation of image deflects and image atomization.

Even the present invention can provide a kind of, have highly stable environmental performance and still can prevent the photoelectric conductor for electronic photography that picture characteristics is deteriorated when reusing for a long time.

In addition, according to the present invention, therefore due to the charge injection that has suppressed to be derived from conductive carrier, even if photoconductor is arranged on while by reversal development (reverse developing process), forming in the device of image, still can obtain extraordinary picture characteristics.

In other words, can limit the deteriorated of individual layer photographic layer or multilayer photographic layer charging property by undercoat, therefore suppress the minimizing of the part surface charges outside the part that should eliminate by exposure, prevent thus the generation of image deflects such as atomization.

Especially, can prevent from being called the image atomization of stain, described stain namely forms on white background in forming image by reversal development toner pore.

The accompanying drawing explanation

Fig. 1 is the figure that shows dip coating apparatus;

Fig. 2 is respectively do for oneself photoelectric conductor for electronic photography (a) and the sectional view (b) of embodiment of the present invention;

Fig. 2 (a) be show the multi-layered type photoconductor comprise middle layer, charge generation layer and three layers of charge transport layer figure and

Fig. 2 (b) is the figure that shows the single-layer type photoconductor that comprises middle layer and photographic layer;

Fig. 3 is the figure that shows the example of image processing system;

Fig. 4 is the X-ray diffraction spectrum that can be used in TiOPc of the present invention; And

Fig. 5 is the X-ray diffraction spectrum that can be used in TiOPc of the present invention.

Embodiment

Term " anhydride silica " for the present invention refers to the silicon dioxide that does not contain water of crystallization.

Term " aqueous silicon dioxide " for the present invention refers to that silicon dioxide is a kind of hydrate, and namely silicon dioxide has water of crystallization.

Hereinafter, the present invention is described in detail with reference to accompanying drawing.

Conductive carrier 2

Conductive carrier also uses as the electrode of photoconductor the support member that acts on each layer.

The constituent material of conductive carrier is not particularly limited, as long as it is what in association area, use.

The instantiation of described constituent material comprises metal and alloy material such as aluminium, aluminium alloy, copper, brass, zinc, nickel, stainless steel, chromium, molybdenum, vanadium, indium, titanium, gold and platinum; With stacked metal forming on substrate surface by being made by cardboard, glass or polymeric material such as polyethylene terephthalate, polyamide, polyester, polyoxymethylene, polystyrene, cellulose and PLA, deposit metallic material or alloy material, or the layer of deposition or coating conductive compound such as conducting polymer, tin oxide, indium oxide and carbon black and the material that obtains.

The example of the shape of described conductive carrier comprises sheet, cylindric, cylindric and endless belt (seamless-band) shape.

As required, can to image quality, not cause in the scope of adverse effect, by anodic oxidation, be coated with processing, use chemicals or the surface treatment of hot water, painted processing or random reflection to process as surface roughening, the surface of conductive carrier is processed.

When using photoconductor of the present invention when using laser as the electrophotographic method of exposure light source, random reflection is processed effective especially.

Namely, because use laser as the electrophotographic method of exposure light source in the wavelength homogeneous of laser, so the laser reflected on photoconductor surface can interfere with the laser in the photoconductor internal reflection, thereby causes presenting interference fringe and produce image deflects on image.In this respect, carry out random reflection processing by the surface to conductive carrier, can prevent the image deflects that may be caused by the interference of the laser with homogeneous wavelength.

Undercoat forms uses coating fluid

In having the performance history of more long-life photoconductor, the present inventor conducts in-depth research, found that, when undercoat contains adhesive resin, utilizes the titania that anhydride silica coats and utilizes the titania that aqueous silicon dioxide coats and the potpourri that preferably utilizes aqueous silicon dioxide and aluminium hydroxide coats titania, even even still can prevent the cohesion of titania and still can obtain stable coating fluid after than conventional storage storage in month longer six months when the dispersion process overtime.

The present inventor also finds, when utilizing above-mentioned undercoat formation to form undercoat with the manufacture photoelectric conductor for electronic photography with coating fluid, reduced the impact of humidity, thereby obtain, there is no the excellent image of stain and atomization under various environment, and can obtain the photoelectric conductor for electronic photography that has long-life more and have improved stability when reusing.

In the situation that contain above-mentioned two kinds of TiO 2 particles, even at the dispersion process overtime, undercoat forms still can prevent the cohesion of titania with coating fluid.As a result, even can obtain after than conventional storage, storing in one month longer six months, still stable coating fluid can be obtained, and the photoelectric conductor for electronic photography with the very uniform coating fluid of undercoat formation use can be obtained.

This is because under low temperature and low humidity environment and hot and humid environment even infer, use has the silicon dioxide of water of crystallization still can make the carrier transport ability in undercoat stable with the combination that does not contain the anhydride silica of water of crystallization, carries charge carrier thereby make it possible to stablize and resist environmental change ground.Yet its detailed mechanism is still unclear.

Propose in addition, by being used in combination aluminium hydroxide, can improve above-mentioned effect.

The undercoat adhesive resin

About the adhesive resin comprised in undercoat, can use and form material identical in the situation of undercoat with the resin individual layer.Its known embodiment comprises polyvinyl resin, acrylic resin, polystyrene resin, acrylic resin, vestolit, vinyl acetate resin, urethane resin, epoxy resin, vibrin, melamine resin, silicones, butyral resin, polyamide, the copolymer resin that comprises two or more these repetitives, casein, gelatin, polyvinyl alcohol (PVA) and ethyl cellulose.In these resins, the polyamide of preferred alcohols dissolubility, butyral resin and vinyl acetate resin, particularly preferably polyamide.

This be because, characteristic as adhesive resin, the solvent that the polyamide comprised in undercoat can not used when forming photographic layer on undercoat occurs to dissolve or swelling, conductive carrier is had to excellent cohesive and flexible, and the metal oxide comprised in undercoat is had to good compatibility, thereby make the metal oxide particle fine dispersion and make dispersion liquid have excellent storage stability.

In polyamide, can use suitably the alcohol soluble nylon resin.

The example of described alcohol soluble nylon resin comprises so-called multipolymer nylon such as the 6-nylon, 6 obtained by copolymerization, 6-nylon, 6,10-nylon, 11-nylon or 12-nylon, and the resin such as the nylon of N-alkoxy methyl modification and the nylon of N-alkoxyethyl modification that obtain by chemical modification nylon.

About undercoat, form the process for dispersing with coating fluid, can use without the ultrasonic dispersion machine of dispersion medium or dispersion machine such as bowl mill, bead mill and the paint regulator of use dispersion medium.Wherein, preferably use the dispersion machine of dispersion medium, utilize described dispersion machine that mineral compound is put into to the solution that adhesive resin is dissolved in organic solvent, and mineral compound is disperseed by the forceful action provided by dispersion machine by means of dispersion medium.

The example of the material of described dispersion medium comprises glass, zircon, aluminium oxide and titanium.Especially, preferably use zirconia and titania, because it has higher wearing quality.

The shape and size of dispersion medium are not limited and the example comprises the pearl with about 0.3mm～5mm size and has the spherical of about 3cm size.

By glass, be not preferred as the dispersion medium material, because in this case, the viscosity of dispersion liquid increases, thereby has reduced storage stability.

This is based on the following fact and considers, when fine metal oxide particles used in to the present invention disperses, by the brute force that dispersion machine provides, not only use the energy of being used as the dispersion of fine metal oxide particles, also as the energy that makes dispersion medium self abrasion, the dispersion medium material that makes the abrasion due to dispersion medium produce is sneaked in the coating dispersion liquid and deteriorated dispersiveness and the storage stability of coating dispersion liquid, thereby coating and the film quality on undercoat has some impact in the formation of the undercoat of photoelectric conductor for electronic photography.

Undercoat forms the solvent with coating fluid

Can be by the organic solvent used in the dispersion liquid of common organic solvent as the undercoat forming photoelectric conductor for electronic photography of the present invention.When using preferred alcohol soluble nylon resin as adhesive resin, can be with an organic solvent if had the lower alcohol of 1～4 carbon atom.

More particularly, undercoat forms and is preferably with the solvent of coating fluid the lower alcohol be selected from methyl alcohol, ethanol, isopropyl alcohol, n-propanol, normal butyl alcohol, isobutyl alcohol and the tert-butyl alcohol.

By polyamide and TiO 2 particles are dispersed in lower alcohol, prepare undercoat and form and use coating fluid, and form described undercoat by coating liquid for undercoat layer being coated on conductive carrier and carrying out drying.

With respect to the titania used, the anhydride silica of cladding titanium dioxide particle surface, aqueous silicon dioxide and aluminium hydroxide separately for the surface-treated use amount, be preferably 0.1 % by weight～50 % by weight.

When anhydride silica, aqueous silicon dioxide and aluminium hydroxide amount separately was less than 0.1 % by weight, the surface of described titania can not fully be coated, thereby was difficult to fully realize the surface-treated effect.

In addition, it is not preferred that anhydride silica, aqueous silicon dioxide and aluminium hydroxide amount separately surpasses 50 % by weight, because in this case, not residual for excessive anhydride silica, aqueous silicon dioxide and the aluminium hydroxide of cladding titanium dioxide and weakened the effect that comprises TiO 2 particles, thereby make described effect basically identical with the effect in the situation that comprises fine particles of silica and aluminium hydroxide, therefore, reduced the susceptibility of photoconductor and the image atomization has occurred.

Preferably, with 10/90～90/10 weight ratio by aqueous silicon dioxide and aluminium hydroxide for the cladding titanium dioxide particle.

More preferably, utilize the surface-treated TiO 2 particles of anhydride silica and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide at least to have the particle diameter of 20nm～100nm.

Simultaneously, when by organic compound such as common coupling agent during for the surface treatment of TiO 2 particles, the resistivity of undercoat is too high, and the susceptibility caused by the impact of humidity although make changes and descends, and susceptibility self is deteriorated and cause the image atomization.

Preferably, do not utilize organic compound if comprised the silane coupling agent of alkoxysilane compound containing trialkylsilyl group in molecular structure; By the atoms such as halogen, nitrogen, sulphur are combined to the silylating reagent obtained with silicon; Phthalate ester coupling agent; With aluminate coupling agent, carry out surface treatment, because in this case, significant image atomization occurs when reusing.

Undercoat (can be called middle layer) 3

For example, by above-mentioned undercoat is formed and is applied on conductive carrier with coating fluid, then filming of obtaining carried out to drying, can access undercoat.

For being coated with described undercoat formation, comprise with the example of the method for coating fluid: the situation at sheet is Baker coating device method, metering bar coater method (for example line rod coating machine method), casting method, spin-coating method, rolling method, knife coating, drop rubbing method, curtain coating method; In the situation of drum, be spray-on process, vertical around-France and dip coating.

As coating process, consider physical property and the throughput rate of coating fluid, can select most suitable method, and particularly preferably dip coating, knife type coater method and spray-on process.

The invention is characterized in, the undercoat that is coated with and forms on the conductive carrier surface contains adhesive resin and utilizes the surface-treated TiO 2 particles of anhydride silica and utilize surface-treated two kinds of particles of TiO 2 particles of aqueous silicon dioxide at least.

Preferably, in the present invention, undercoat contains and utilizes the surface-treated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and two kinds of particles of TiO 2 particles that the aluminium hydroxide surface both was processed.

Preferably, in the present invention, TiO 2 particles has the average primary particle diameter of 20nm～100nm.

Preferably, in the present invention, with 80/20～30/70 weight ratio, use and utilize the surface-treated TiO 2 particles of anhydride silica and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide.

Preferably, in the present invention, utilizing the surface-treated TiO 2 particles of aqueous silicon dioxide is the TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process.

Preferably, in the present invention, utilizing the surface-treated TiO 2 particles of aqueous silicon dioxide is the TiO 2 particles that utilizes the mixture process of the aqueous silicon dioxide that mixes with 10/90～90/10 weight ratio and aluminium hydroxide to cross.

Preferably, in the present invention, with respect to adhesive resin, use TiO 2 particles with 10/90～95/5 weight ratio.

Preferably, in the present invention, described adhesive resin is polyamide.

Preferably, in the present invention, undercoat has the film thickness of 0.05 μ m～5 μ m.

Undercoat has and prevents that electric charge is injected into function individual layer photographic layer or multilayer photographic layer (barrier injected as hole) from conductive carrier.

In other words, by undercoat, limit charging property deteriorated of individual layer photographic layer or multilayer photographic layer, therefore, limited the minimizing of the part surface charges outside the part that will eliminate by exposure electric charge, thus the image deflects of preventing such as atomization.

Especially, can prevent from being called the image atomization of stain, described stain namely forms in image forms by reversal development on white background toner pore.

The undercoat of coated with conductive carrier surface can reduce concavo-convex degree, thereby make uniform surface, improved the film forming characteristics of individual layer photographic layer or multilayer photographic layer, and improved the adhesiveness (cohesive) between conductive carrier and individual layer photographic layer or multilayer photographic layer, described concavo-convex be the defect on conductive carrier surface.

Photoelectric conductor for electronic photography with above-mentioned undercoat can prevent the image deflects that caused by the defect of conductive carrier, and between conductive carrier and photographic layer, keeps predetermined electrical characteristics simultaneously.

Especially, by use, organic material such as the phthalocyanine color that longer wavelength has light sensitivity had to the photoelectric conductor for electronic photography of excellent undercoat with manufacture as charge generating material, and by this photoelectric conductor for electronic photography being arranged in the image processing system that adopts reversal development, make the picture characteristics excellence, and do not contain pore that cause because of reducing or eliminating of surface charge in tiny area, on the peculiar white background of discharged-area development.

Described photoelectric conductor for electronic photography be characterised in that its comprise conductive carrier, at the undercoat formed on described conductive carrier and the photographic layer that forms on described undercoat, and described undercoat has the film thickness of 0.05 μ m～5 μ m.

For conventional undercoat, reduce film thickness and can improve environmental characteristics but can reduce bonding between conductive carrier and photographic layer, thereby cause the adverse effect that produces image deflects because of the defect of conductive carrier.

On the other hand, increase film thickness meeting desensitising the deteriorated environmental characteristics of undercoat.Therefore, be used to realizing that both actual membrane thickness of the stability that reduces image deflects and improve electrical characteristics is restricted.

Yet, the present inventor has been found that, when containing, undercoat utilizes the surface-treated TiO 2 particles of anhydride silica and while utilizing two kinds of particles of the surface-treated TiO 2 particles of aqueous silicon dioxide, can improve the dispersiveness in undercoat, can prevent the generation of condensation product, filming can be smooth and have the resistance of even maintenance, and can obtain and be difficult for because of environmental change through affecting adversely and potential property and the picture characteristics of stable photoconductor under various environment.

Photoelectric conductor for electronic photography of the present invention can suppress the fluctuation of the fluctuation of photoconductor microscopic characteristics, particularly susceptibility and rest potential, thus the generation of the image deflects of preventing and image atomization.

Described photoelectric conductor for electronic photography is characterised in that, the adhesive resin comprised in undercoat is the polyamide of organic solvent solubility.

Because the polyamide of the adhesive resin as comprising in undercoat is easy to the metal oxide particle coupling and also with conductive carrier, has excellent adhesiveness, can keep the flexible of film so contain the undercoat of polyamide.

In addition, the coating fluid that the polyamide comprised in the undercoat formed is being used to form photoconductor is not with can swelling or dissolving in solvent, thereby prevented defect in the undercoat and the generation of inhomogeneous coating, therefore can provide the electrofax photoconduction that shows the excellent image characteristic.

The crystal formation of described titania can be rutile-type, Detitanium-ore-type, any type in amorphous, or is the two or more potpourri of these types.The shape of titania used is generally granular, but can be needle-like or dendroid.

For the term used herein " needle-like " of mineral compound crystalline form, refer to and comprise bar-shaped, column and fusoid elongated shape; It needn't be located sharply extremely elongated or endways.

In addition, the invention is characterized in, utilize the surface-treated TiO 2 particles of anhydride silica and utilize the surface-treated TiO 2 particles of aqueous silicon dioxide at least both to have the average primary particle diameter of 20nm～100nm.

Titania with this average primary particle diameter has good dispersiveness and therefore can be dispersed in adhesive resin.

The average primary particle diameter of the titania therefore, comprised in undercoat is preferably in 20nm～100nm scope.

Based on SEM (S-4100, by high-tech Co., Ltd. of Hitachi (Hitachi High-Technologies Corporation) manufacture) photo, the particle diameter of 50 above particles is measured and averaged to determine titania or utilize the average primary particle diameter of the surface-treated titania of the anhydride silica titania surface-treated with utilizing aqueous silicon dioxide at least.

Described average primary particle diameter is below 20nm, to be not preferred, because in this case, dispersiveness may differ from and cause and condense and improve viscosity, thereby causes the solution deficient in stability.

In addition, the undercoat that viscosity is increased form with coating fluid, be applied on conductive carrier very difficult, thereby cause producing rate variance.

In addition, described average primary particle diameter is more than 100nm, to be not preferred, because in this case, during the formation of undercoat, the charging property in tiny area descends, and is easy to produce stain thereby make.

Utilizing the surface-treated TiO 2 particles of anhydride silica and utilizing the surface-treated total content of TiO 2 particles in undercoat of aqueous silicon dioxide at least is 10 % by weight～99 % by weight, preferably 30 % by weight～99 % by weight, more preferably 35 % by weight～95 % by weight.

When the content of titania was less than 10 % by weight, susceptibility descended, charge generation accumulation in undercoat and improved rest potential.Particularly under the low temperature and low humidity environment, this phenomenon is more remarkable aspect Repeatability.

On the other hand, it is not preferred that the content of titania surpasses 99 % by weight, because in this case, in undercoat, is easy to produce condensation product and be easy to produce image deflects.

The powder volume resistance of described TiO 2 particles is preferably 10 ⁵Ω cm～10 ¹⁰Ω cm.

When powder volume resistance is less than 10 ⁵During Ω cm, descend and make undercoat can not serve as electric charge barrier layer as the resistance of undercoat resistance.

For example, having experienced conductive processing as very low doped with the powder volume resistance of the inorganic compound particles of the fin oxide condutire layer of antimony as formation, is 10 ⁰Ω cm～10 ¹Ω cm.The undercoat that uses this conductive layer is out of use, because it does not serve as electric charge barrier layer and occurs deteriorated and produce image atomization and stain as the charging property of photoconductor characteristic.

On the other hand, the powder volume resistance of TiO 2 particles surpasses 10 ¹⁰Ω cm, be that the volume resistance that the powder volume resistance of TiO 2 particles is equal to or greater than adhesive resin is not preferred, because in this case, resistance as undercoat resistance is too high, make the conveying of the charge carrier produced when exposure be suppressed, thereby increased rest potential and reduced light sensitivity.

In addition, for the present invention's TiO 2 particles for utilizing the surface coated TiO 2 particles of anhydride silica and utilizing the surface coated TiO 2 particles of aqueous silicon dioxide at least.

More preferably, the TiO 2 particles for the present invention is to utilize the surface coated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and the TiO 2 particles of aluminium hydroxide surface both coating.

When using surperficial untreated TiO 2 particles, even TiO 2 particles is well dispersed in coating fluid, with TiO 2 particles described in the situation of coating fluid, because of its micron-scale, be easy to cohesion in long-term use or the formation of storage undercoat.In this case, this cohesion is inevitable.

Therefore, utilize the undercoat contain surperficial untreated TiO 2 particles and to carry out standing storage to form to form undercoat with coating fluid to cause producing defect and the unevenness of filming, thus the image deflects of causing.

In addition, because making, this defect in filming and inhomogeneous coating be easier to from the conductive carrier iunjected charge, so the charging property in tiny area descends and produces stain.

Routinely, attempted improving the dispersiveness in undercoat by utilizing aluminium oxide to carry out surface treatment to TiO 2 particles.Yet, in this case, and when by dip coating, forming undercoat on the drum as conductive carrier (dram), must a large amount of coating fluid of preparation.Therefore, in long-time, implement dispersion process and can cause the cohesion again of titania and produce stain, thereby cause image quality to descend.

It is believed that, because long dispersion process causes peeling off for the surface-treated aluminium oxide, thereby reduced the surface-treated effect and made titania condense again, cause thus image deflects and promoted to be derived from the charge injection of conductive carrier, thereby reduced the charging property in the undercoat tiny area and produced stain.

In addition, while under hot and humid environment, using for a long time, this stain is more remarkable, thereby causes image quality greatly to descend.

In some other situation, utilize the magnetic metal oxide of tool such as Fe ₂O ₃Come the cladding titanium dioxide surface.This is not preferred, because of the phthalocyanine color generation chemical reaction comprised in metal oxide and photographic layer, has reduced the characteristic of photoconductor, particularly causes susceptibility to descend and charging property decline.

The present invention can provide a kind of photoelectric conductor for electronic photography, described photoelectric conductor for electronic photography is not subject to the impact of humidity and under various environment, can produces the excellent image that there is no stain and image atomization, and described photoelectric conductor for electronic photography contains and utilizes the surface coated TiO 2 particles of anhydride silica and utilize the undercoat of two kinds of particles of the surface coated TiO 2 particles of aqueous silicon dioxide at least by formation, preferably by formation, contain and utilize the surface coated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and the undercoat of two kinds of particles of TiO 2 particles that surface of aluminum hydroxide coats and have the stability of raising when reusing.

Routinely, use and only utilize the surface coated TiO 2 particles of anhydride silica with acquisition, to have the photoconductor of better stability.Yet when the life-span of attempting to extend this photoconductor (this is that recent photoconductor is desired), after under hot and humid environment, reusing for a long time, described photoconductor experience susceptibility changes.

Simultaneously, in using and only utilizing the situation of the surface coated TiO 2 particles of aqueous silicon dioxide, the susceptibility of described photoconductor occurs deterioratedly usually under the low temperature and low humidity environment, and provides poor image quality as low image density.

In addition, in the present invention, can prevent that the charge injection that is derived from conductive carrier has the photoelectric conductor for electronic photography of the improvement picture characteristics that does not contain stain with acquisition.In addition, even when under the low temperature and low humidity environment and under hot and humid environment, reusing, susceptibility still can not change, and can obtain the improved picture characteristics that there is no stain and image atomization.

When long-term use photoconductor, especially, paper, travelling belt, toner etc. contact with photographic layer and cause wearing and tearing, thereby have reduced the film thickness of photographic layer.In this case, environmental change such as low temperature and low humidity and hot and humid and for example, because of the insulation breakdown in tiny area and the nonuniform film in undercoat zone (, part is present in condensation product and the impurity of the metal oxide in undercoat), have generation and an increase that the local zone descended of volume resistance causes stain and image atomization.Yet, even under the limiting film thickness degree of the end of life as photoconductor (even when when the voltage on being applied to charged device changed, the surface potential on photoconductor also no longer changed the film thickness of photoconductor), the present invention also can provide the excellent image characteristic that there is no stain and image atomization.

The film thickness of described undercoat is preferably 0.01 μ m～10 μ m, more preferably in the scope of 0.05 μ m～5 μ m.

When the film thickness of undercoat was less than 0.01 μ m, described film can not serve as undercoat basically, therefore can not obtain uniform surface by the defect that covers conductive carrier, thereby can not prevent from being derived from the carrier injection of conductive carrier and cause charging property deteriorated.

In addition, it is not preferred that the film thickness of undercoat surpasses 10 μ m, because in this case, is difficult to manufacture photoconductor by the dip coating painting bottom coating, and the susceptibility of photoconductor descends.

Photographic layer 4

The structure of the photographic layer formed on undercoat can be divided for function divergence type (multilayer) photographic layer that formed by charge generation layer 5 and 6 two layers of charge transport layer or be formed and the individual layer photographic layer of the separative charge generation layer of tool and charge transport layer not by single layer, can use any one in them.

Next, with reference to accompanying drawing, photoconductor of the present invention is elaborated.

Fig. 2 is the schematic sectional view of structure that shows the necessary part of multi-layered type photoconductor of the present invention (a) and single-layer type photoconductor (b).

Fig. 2 (a) is the schematic sectional view of structure that shows the necessary part of multi-layered type photoconductor, and wherein photographic layer 4 is the multilayer photographic layers (also referred to as " function divergence type photographic layer ") that form by stack gradually charge generation layer and charge transport layer on undercoat 3.

Fig. 2 (b) is the schematic sectional view of structure that shows the necessary part of single-layer type photoconductor, and wherein photographic layer 4 is the individual layer photographic layers that formed by individual layer stacking on undercoat 3.

In multilayer photographic layer in Fig. 2 (a), can form in reverse order charge generation layer 5 and charge transport layer 6, but preferably wherein with the order shown in Fig. 2 (a), form the multilayer photographic layer of described two layers.

In multi-layered type photoconductor 1a in Fig. 2 (a), on the surface of conductive carrier 2, stack gradually undercoat 3 and multilayer photographic layer 4, wherein in described multilayer photographic layer 4, stack gradually the charge generation layer 5 that contains charge generating material 8 and adhesive resin 7 and contain charge transport material 18 and the charge transport layer 6 of adhesive resin 9.

In single-layer type photoconductor 1b in Fig. 2 (b), on the surface of conductive carrier 2, form successively undercoat 3; With the individual layer photographic layer 4 that contains charge generating material 8, charge transport material 19 and adhesive resin 9.

Photographic layer 4 in multi-layered type photoconductor 1a

Photographic layer 4 in multi-layered type photoconductor 1a is formed by charge generation layer 5 and charge transport layer 6.By charge generation function and charge transport function are assigned to layer separately, can select independently to be used to form the optimal material of each layer.

Hereinafter, will be to by stacking gradually the multi-layered type photoconductor (Fig. 2 (a)) that charge generation layer and charge transport layer form, describing.Yet except the stacking order difference, described explanation also is suitable for the multi-layered type photoconductor of reverse double deck type.

Herein, in the situation that single layer structure or sandwich construction, for photographic layer preferably, described undercoat injects and to play barrier action for the hole from conductive carrier, and following photographic layer 4 and the photographic layer 4 in single-layer type photoconductor 1b in multi-layered type photoconductor 1a is electronegative to have high sensitive and high-durability.

Charge generation layer 5

In the situation of function divergence type photographic layer, on undercoat, form charge generation layer.The known embodiment of the charge generating material comprised in charge generation layer comprises bis-azo compound such as chloranil (chloro dian blue), polynucleation quinone compound such as dibromo anthanthrone, perylene compound, quinacridone compound, phthalocyanine compound and Azulene (azulenium) salt compound.Require charge generating material by reversal development, using laser beam or LED in 620nm～800nm long wavelength's scope, to have susceptibility in as light source, forming the photoelectric conductor for electronic photography of image.

As the charge generating material for this purpose, phthalocyanine color and trisazo pigment have been considered, because it has high sensitive and excellent permanance.Especially, phthalocyanine color also has excellent characteristic, and can use one or more pigment separately or in the mode of combination.

The example of spendable phthalocyanine color comprise metal-free phthalocyanine and metal phthalocyanine, with and composition thereof with the mixed grain effect compound.

The example that can be used for the metal of metal phthalocyanine pigment comprises that oxidation state is zero metal, metal halide such as chloride and bromide and oxide.The preferred embodiment of metal comprises Cu, Ni, Mg, Pb, V, Pd, Co, Nb, Al, Sn, Zn, Ca, In, Ga, Fe, Ge, Ti and Cr.Although proposed multiple technologies, using manufacture method as these phthalocyanine colors, can use any manufacture method.For example, can make with the following method: after being prepared into pigment, phthalocyanine is carried out various purifications or utilizes various organic solvents to carry out dispersion treatment with the conversion crystal formation to it.

In the present invention, phthalocyanine is used as to the charge generating material comprised in charge generation layer.Preferably, can suitably use τ type metal-free phthalocyanine; In X-ray diffraction spectrum, locate to have the crystal-type TiOPc at maximum diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 27.3 °; Or at least in X-ray diffraction spectrum the Bragg angle (2 θ ± 0.2 °) 7.3 °, 9.4 °, 9.7 ° and 27.3 ° locate to have diffraction peak, wherein at 9.4 ° and 9.7 ° of diffraction peaks of locating bifurcated peak and than large 27.3 ° of diffraction peaks of locating clearly both, and at 9.4 ° of diffraction peaks of locating crystal-type TiOPc that is maximum diffraction peaks.

Use has the crystal-type TiOPc at this specific X-ray diffraction peak, the high sensitive when long-term use is provided and in hot and humid improved electrical characteristics under all environment of low temperature and low humidity.

The basic structure of TiOPc is by following general formula:

X wherein ₁～X ₄Mean separately halogen atom, C ₁-C ₄Alkyl or C ₁-C ₄Alkoxy, and k, l, m and n mean 0～4 integer separately.

Described halogen atom is fluorine, chlorine, bromine or iodine atom; Described C ₁-C ₄Alkyl is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl or the tert-butyl group; And described C ₁-C ₄Alkoxy is methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy.

Can be by any method as at Moser and Thomas " Phthalocyanine Compounds " (" phthalocyanine compound ") (Moser and Thomas. " Phthalocyanine Compounds ", Reinhold Publishing Corp., New York, 1963) in, disclosed known method carrys out synthetic phthalocyanine oxygen titanium.For example,, by by phthalonitrile and titanium tetrachloride heat fused or under the existence of organic solvent such as α-chloronaphthalene, it is heated and can obtain with good yield dichloro titanium-phthalocyanine.In addition, by utilizing alkali or water to be hydrolyzed and can to access TiOPc dichloro titanium-phthalocyanine.The TiOPc made can contain hydrogen atom in phenyl ring wherein and be substituted the phthalocyanine derivates that base such as chlorine, fluorine, nitro, cyano group and sulfuryl replace.

Under the existence of water, utilize with the immiscible organic solvent of water such as ethylene dichloride this TiOPc composition is processed to obtain crystal formation of the present invention.

Under the existence of water, utilize the limiting examples of the method for TiOPc being processed with the immiscible organic solvent of water to comprise to utilize water to make the TiOPc swelling and utilize method that organic solvent processes and to add in organic solvent water and not the TiOPc powder of swelling put into method wherein.

Utilize water that the limiting examples of the method for TiOPc swelling is comprised and will in the TiOPc vitriolization and in water, be deposited as the method for wet paste form; With utilize water to make the TiOPc swelling and use to stir or diverting device such as mixer for well-distribution, paint mixer, bowl mill and side grinding machine (side mill) form it into the method for wet paste.

In addition, by stirring the sufficiently long time or applying mechanical stress, the TiOPc composition that hydrolysis obtains is ground, thereby obtain crystal formation of the present invention.

Except common stirring apparatus, the example that can be used for the device of this processing comprises mixer for well-distribution, paint mixer, decollator, AJITER, bowl mill, side grinding machine, masher and ultrasonic diverting device.After processing, implement to filter; Utilize methyl alcohol, ethanol, water etc. to wash; And separate.

The TiOPc obtained by this way demonstrates the excellent specific property as the charge generating material of photoelectric conductor for electronic photography.In the present invention, other charge generating materials can be used together with above-mentioned TiOPc.The example of other charge generating materials comprises α-type, β-type, Y-Shaped and amorphous TiOPc, and its crystal formation from TiOPc of the present invention is different; Other phthalocyanine; AZO pigments; Fear quinone pigments; Perylene pigment; Many ring quinone pigments; With square acid color.

The example that uses these phthalocyanine colors to prepare the method for charge generation layer comprises charge generating material, particularly phthalocyanine color is carried out to vacuum-deposited method; And charge generating material is mixed with adhesive resin and organic solvent, and be dispersed in the method that wherein forms film, can use before this muller in advance charge generating material to be ground.The example of muller comprises bowl mill, sand mill, masher, vibration mill and ultrasonic diverting device.

Usually, the method that preferably charge generating material is dispersed in binder resin solution and then is coated with.The example of described coating process comprises spray-on process, excellent painting method, rolling method, knife coating, around-France and dip coating.

Dip coating is following method: conductive carrier is immersed and is equipped with in the coating pan of coating fluid, then under constant rate of speed or under the speed that order changes, it is mentioned, thereby form layer on described conductive carrier.Because dip coating is relatively simple and aspect throughput rate and manufacturing cost excellence, therefore usually by the method for the manufacture of photoconductor.Device for dip coating can be provided with the coating fluid diverting device by the ultrasonic generator representative, thereby stablizes the dispersiveness of coating fluid.

Especially, dip coating is relatively simple and favourable aspect throughput rate and cost as shown in Figure 1, therefore, usually uses it for the manufacture photoelectric conductor for electronic photography.In described dip coating, the conductive carrier immersion is equipped with to photoconductor formation uses coating fluid such as charge generation layer formation to use in the coating pan of coating fluid with coating fluid or the formation of individual layer photographic layer with coating fluid, charge transport layer formation, then under the speed of constant rate of speed or order variation, it is mentioned, form thus photographic layer.

In the dip coating apparatus shown in Fig. 1, more specifically, coating liquid bath 13 and tank diameter 14 are equipped with coating fluid 12.Effect by engine 16, by circulation passage 17, coating fluid 12 is sent to coating liquid bath 13 from tank diameter 14, then the slope cyclic passage 17b that is coated with liquid bath 13 tops and tank diameter 14 tops by connection is sent to tank diameter 14 by it from coating liquid bath 13, circulates thus.

Above coating liquid bath 13, conductive carrier 2 is connected on turning axle 10.The axial vertical direction along described coating liquid bath 13 of described turning axle 10, and make turning axle 10 rotations by the effect of engine 11, thus the carrier be connected thereto 2 is moved up and down.Engine 11 rotates with a predetermined direction, thereby makes carrier 2 move downward and immerse in the coating fluid 12 of coating in liquid bath 13.

Then, engine 11 is with another direction rotation with above-mentioned opposite direction, makes carrier 2 move upward and leaves coating fluid 12 dry to form the film of coating fluid 12.

Especially, dip coating is relatively simple and favourable aspect throughput rate and cost as shown in Figure 1, therefore, usually uses it for the manufacture photoelectric conductor for electronic photography.In dip coating, conductive carrier is immersed and photoconductor formation is housed with in the coating pan of coating fluid, the speed then changed with constant rate of speed or order is mentioned, and forms thus photographic layer.

Can be used for photoconductor and form the copolymer resin that example with the adhesive resin of coating fluid comprises melamine resin, epoxy resin, silicones, urethane resin, acrylic resin, polycarbonate resin, polyarylate resin, phenoxy resin, butyral resin and comprises two or more these repetitives, for example insulating resin such as vinyl chloride vinyl acetate copolymer resin and acrylonitritrile-styrene resin resin.Adhesive resin is not limited to these resins, and can use normally used all resins separately or in the mode of its two or more combinations.

The example that dissolves the solvent of these resins comprises halogenated hydrocarbons such as methylene chloride and ethylene dichloride; Ketone such as acetone, methyl ethyl ketone and cyclohexanone; Ester class such as ethyl acetate and butyl acetate; Ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; With aprotic polar solvent such as DMF and DMA, and the mixed solvent of these solvents.

Preferably, phthalocyanine color and adhesive resin are carried out to blend, make the ratio of phthalocyanine color in the scope of 10 % by weight～99 % by weight.When the ratio of phthalocyanine color be less than this scope lower in limited time, susceptibility reduces.When the ratio of phthalocyanine color surpass this scope upper in limited time, dispersed decline and cause oversize grain to increase, thus produce more image deflects, particularly more stain.

In order to prepare charge generation layer formation, use coating fluid, phthalocyanine color is mixed with adhesive resin and organic solvent, then phthalocyanine color is dispersed in wherein.For dispersion, can select suitable condition, thereby prevent the contaminating impurity that solution is produced by wearing and tearing because of container used and diverting device etc.

Must by the phthalocyanine color comprised in the dispersion liquid obtained as mentioned above be dispersed to make primary particle diameter and/or the cohesion particle diameter be the degree below 3 μ m.

While being greater than 3 μ m, in the situation of discharged-area development, the gained photoelectric conductor for electronic photography can produce a large amount of stains on white background when elementary particle diameter and/or cohesion particle diameter.Therefore, when utilizing various diverting devices to prepare charge generation layer, form while using coating fluid, dispersion condition is optimized, makes the phthalocyanine color particle is separated into and has the preferably particle diameter below 3 μ m, more preferably following median particle diameter and the following mode particle diameter of 3 μ m of 0.5 μ m.Preferably, do not contain the particle that is greater than above-mentioned particle diameter.

Because the particulate of phthalocyanine color particle requires more intense dispersion condition and longer jitter time because of their chemical constitution, it is inevitable so further disperse, causing the cost poor efficiency and make the pollution of the impurity caused by the wearing and tearing of dispersion medium.

In addition, further disperse to cause to make the crystal formation of phthalocyanine color particle change because of during dispersion organic solvent and heat or the impact that causes because of dispersion, thereby the susceptibility had a negative impact as photoconductor descends greatly.Therefore, not preferably, make the phthalocyanine color particle diminish as having median particle diameter and the mode particle diameter below 0.1 μ m below 0.01 μ m.

Phthalocyanine color particle in being dispersed in coating fluid comprises while having the particle that is greater than 3 μ m particle diameters, can remove having the primary and/or the aggregated particle that are greater than 3 μ m particle diameters by filtering.As the filter material that is ready to use in filtration, can use common material, as long as they swelling can not occur or dissolve in being ready to use in the organic solvent of dispersion, and preferably use Teflon (registered trademark) film filter with uniform pore size.In addition, by centrifuging, can remove oversize grain and condensation product.

In the present invention, use to utilize by the charge generation layer obtained as mentioned above and form with the formed charge generation layer of coating fluid, make film preferably have the thickness of 0.05 μ m～5 μ m, more preferably have the thickness of 0.08 μ m～1 μ m.

When in the conventional structure at undercoat and photographic layer, increasing the film thickness of charge generation layer, although improved sensitivity characteristic, can have a negative impact and namely produce image deflects if because in tiny area, eliminating surface charge, on white background, produced pore.

On the other hand, when the film thickness of undercoat reduced, susceptibility descended.Therefore, limited and can reduce image deflects and improve between electrical characteristics and production stability and realize well balanced actual membrane thickness.

Yet, because containing metal oxide particle, particularly the present invention, use utilize the undercoat of the surface-treated TiO 2 particles of anhydride silica to improve the dispersiveness in undercoat, so can prevent the generation of condensation product and film can be smooth and have the resistance of even maintenance.Therefore as a result, can evenly keep the microscopic characteristics, particularly susceptibility of photoconductor and the fluctuation of rest potential, even when increasing the film thickness of charge generation layer, still can suppress the generation of image deflects and image atomization.In addition, due to the film thickness that can increase charge generation layer, so can realize higher susceptibility.

The film thickness of charge generation layer is not preferred lower than above-mentioned scope, because it not only causes susceptibility to descend, also causes because disperseing the very little variation that causes crystal formation until its particle becomes to phthalocyanine color.

Although the film thickness of charge generation layer surpasses above-mentioned scope, provide specific susceptibility, aspect cost be difficult to evenly be coated with aspect, be also not preferred.

Charge transport layer 6

For the manufacture of the representative instance of the method that is arranged on the charge transport layer on charge generation layer, comprise by charge transport material is dissolved in binder resin solution and prepare charge transport layer and form and use coating fluid, and described coating fluid is coated with and forms the method for film.

The known embodiment of the charge transport material comprised in charge transport layer comprises hydrazone compound, pyrazoline compounds, triphenyl amine compound, triphenyl methane compound, 1, the 2-diphenyl ethene compounds and

Diazole compounds, it can use separately or in the mode of its two or more combinations.

As adhesive resin, can use one or more resins mentioned to charge generation layer separately or in the mode of combination.In order to manufacture charge transport layer, can use the method identical with undercoat.

The film thickness of described charge transport layer is preferably in 5 μ m～50 μ m scopes, more preferably in 10 μ m～40 μ m scopes.

Photographic layer 4 in single-layer type photoconductor 1b

Described individual layer photographic layer comprises charge generating material, charge transport material and adhesive resin (bonding agent) and usings as its principal ingredient.

Described individual layer photographic layer can the appropriate amount in the scope of not damaging effect of the present invention optionally comprise with charge generation layer in the identical adjuvant that comprises.

Can be by charge generating material, charge transport material and other optional adjuvants being dissolved and/or being dispersed in suitable organic solvent to prepare individual layer photographic layer formation coating fluid, described coating fluid is applied on the surface of the undercoat formed on conductive carrier, then it is carried out to drying to remove organic solvent, form described individual layer photographic layer.

Other steps of using and condition be used to form the consistent of charge generation layer and charge transport layer.

Although be not particularly limited, the film thickness of described individual layer photographic layer is preferably 5 μ m～50 μ m, particularly preferably 10 μ m～40 μ m.

When the film thickness of individual layer photographic layer was less than 5 μ m, the electric charge hold facility of photoconductor surface may descend.When the film thickness of individual layer photographic layer surpassed 50 μ m, throughput rate may descend.

In order to improve susceptibility and to reduce because reusing rest potential and the fatigue caused, can in photographic layer, add one or more electronics acceptor materials.The example comprises quinones such as 1,4-benzoquinone, tetrachloroquinone, tetrachloro-1,2-benzoquinones, quinhydrones, 2,6-phlorone, methyl isophthalic acid, 4-benzoquinones, α-naphthoquinone and beta-naphthoquinone; Nitro compound is as 2,4,7-trinitro--9-Fluorenone, 1,3,6,8-tetranitrocarbazol, to nitro benzophenone, 2,4,5,7-tetranitro-9-Fluorenone and 2-nitryl fluorenone; With cyano compound such as TCNE, 7,7,8,8-four cyano quino bismethane, 4-(p-nitrophenyl formyloxy)-2 ', 2 '-dicyano vinyl benzene and 4-(m-nitro formyloxy)-2 ', 2 '-the dicyano vinyl benzene.

Among above-mentioned substance, particularly preferably have electron-withdrawing substituent such as Cl, CN and NO ₂Fluorenone compound, naphtoquinone compounds and benzene derivative.In addition, photographic layer can contain ultraviolet light absorber and antioxidant such as benzoic acid; 1,2-diphenyl ethene compounds and derivant thereof; With nitrogenous compound such as triazole compounds, imidazolium compounds,

Diazole compounds and thiazolium compounds and derivant thereof.

The protective seam (not shown)

Photoconductor of the present invention can have the protective seam (not shown) on the surface of the photographic layer 4 of multi-layered type photoconductor 1a or on the surface at the photographic layer 4 of single-layer type photoconductor 1b.

Described protective seam has the wearing quality that improves photographic layer and prevents the function of the chemical adverse effect caused because of ozone and oxides of nitrogen.

In addition, if necessary, the surface of protective seam for the protection of photographic layer can be set.

Can be by thermoplastic resin and light or heat reactive resin for sealer.In addition, described sealer can contain ultraviolet protecting agent, antioxidant, inorganic material such as metal oxide, organometallics and electronics acceptor material.

For example; by adhesive resin and needed adjuvant such as antioxidant and ultraviolet light absorber being dissolved or being dispersed in suitable organic solvent to prepare protective seam, form and use coating fluid; and described protective seam is formed and is applied on the surface of individual layer photographic layer or multilayer photographic layer with coating fluid; then it is carried out to drying to remove organic solvent, can form protective seam.Those in the formation of other steps of using and condition and charge generation layer are consistent.

Although be not particularly limited, the film thickness of protective seam is preferably 0.5 μ m～10 μ m, particularly preferably 1 μ m～5 μ m.The film thickness of described protective seam is less than 0.5 μ m can cause wearing no resistance of photoconductor surface and permanance deficiency.On the other hand, the film thickness of protective seam surpasses the resolution that 10 μ m can reduce photoconductor.

In addition; if necessary; photographic layer and protective seam optionally can be mixed with plastifier such as dibasic acid ester, fatty acid ester, phosphate, phthalic ester and chlorinated paraffin; so that mechanical property improves; thereby give processability and flexible, or photographic layer and protective seam and leveling agent such as silicones can be carried out to blend.

Photoelectric conductor for electronic photography of the present invention can be used for to electrophotographic copier, and have in laser instrument or the various printers and electrofax forme-producing system of light emitting diode (LED) as light source.

Image processing system 20

Image processing system 20 of the present invention comprises at least: photoconductor 21 of the present invention; For making the charged charged means of described photoconductor (means claims again " unit "); Described charged photoconductor is exposed to form to the exposure means of electrostatic latent image; The development means of the electrostatic latent image formed by exposure being developed to form to toner image; To be transferred to by the toner image that development forms the transfer printing means on recording medium; With the toner image to being transferred on recording medium, carry out photographic fixing to form the photographic fixing means of image.

With reference to accompanying drawing, image processing system of the present invention is described, but the invention is not restricted to following explanation.

Fig. 3 is the schematic side elevation of the structure of demonstration image processing system of the present invention.

Image processing system 20 in Fig. 3 (for example comprises photoconductor 21 of the present invention, photoconductor 1a and 1b shown in Fig. 2 (a) and 2 (b)), charged means (charged device) 24, exposure means 28, development means (developing cell) 25, transfer printing means (transfer printing unit) 26, cleaning means (clearer) 27, photographic fixing means (fixation unit) 31 and except electric hand section (not shown, as to be connected on cleaning means 27).Reference numeral 30 means transfer paper.

By the unshowned main body of image processing system 20, rotatably support photoconductor 21 and drive described photoconductor 21 so that it rotates on arrow 23 directions around turning axle 22 by unshowned driving means.For example, described driving means has the structure that comprises motor and reduction gearing, and its driving force is passed to the conductive carrier of the core body that forms photoconductor 21, drives thus described photoconductor 21 under predetermined circle speed, to rotate.Along the outer peripheral face of photoconductor 21, on the sense of rotation of pressing the photoconductor 21 shown in arrow 23, from the upstream side to the downstream, arrange successively charged device 24, exposure means 28, developing cell 25, transfer printing unit 26 and clearer 27.

Described charged device 24 is for making the charged charged means to predetermined potential of outer peripheral face of described photoconductor 21.Particularly, by for example contact-type charged roller 24a, band brush or charged device wire such as corona tube or scorotron, realize charged device 24.Reference numeral 24b means grid bias power supply.

Described exposure means 28 for example has the semiconductor laser as light source, and apply from the charged device 24 of photoconductor 21 and the laser 28a of the output of the light source between developing cell 25, thereby expose according to the outer peripheral face of image information to charged photoconductor 21.On the direction that the turning axle 22 that main scanning direction is photoconductor 21 extends, repeat to transmit light 28a to scan, thereby order forms electrostatic latent image on the surface of described photoconductor 21.

The development means that described developing cell 25 develops for the electrostatic latent image that utilizes developer to form exposure on the surface by photoconductor 21.With in the face of the mode of described photoconductor 21, arrange described developing cell 25 and described developing cell 25 have to the developer roll 25a of the outer peripheral face supplying toner of described photoconductor 21 with can around this mode of the parallel turning axle rotation of the turning axle 22 with photoconductor 21, supporting the box 25b of described developer roll 25a, described box 25b holds the developer that contains toner in the section space within it.

Transfer printing unit 26 is for for toner image namely is transferred to the transfer printing means on transfer paper 30 by development at the visual picture formed on the outer peripheral face of photoconductor 21, the recording medium of described transfer paper 30 for supplying between photoconductor 21 and transfer printing unit 26 from the direction of arrow 29 by unshowned transmission means.For example, described transfer printing unit 26 is non-contact type transfer printing means, and it comprises charged means and by for transfer paper 30, providing with the opposite polarity electric charge of toner charge, toner image is transferred on transfer paper 30.

Described clearer 27 is after by transfer printing unit 26, implementing transfer operation, by the cleaning means that the toner remained on photoconductor 21 outer peripheral faces is removed and collected, described clearer 27 comprises the cleaning blade 27a that peels off for the toner that will remain on photoconductor 21 outer peripheral faces and be used to holding the disposable box 27b of the toner of peeling off by cleaning blade 27a.This clearer 27 and the unshowned electric light that removes are arranged together.

Described image processing system 20 also has fixation unit 31, described fixation unit 31 for the downstream of the transfer paper 30 that is transmitted between by photoconductor 21 and transfer printing unit 26 by the photographic fixing means of the image fixing of transfer printing.Described fixation unit 31 comprises the warm-up mill 31a with unshowned heater means, thereby and is arranged on described warm-up mill 31a opposite side by warm-up mill 31a and compresses the backer roll 31b that forms adjacency section.

By if got off, implementing to form by image processing system 20 operation of images.At first, by driving means, drive photoconductor 21 so that it rotates on the direction of arrow 23, then, by charged device 24, that the surface uniform of photoconductor 21 is charged to predetermined positive potential or negative potential, wherein with respect to the image of the light 28a applied by exposure means 28, form point, at the upstream side of photoconductor 21 sense of rotation, described charged device 24 is set.

Then, according to image information, utilize the light 28a that exposure means 28 is launched to irradiate the surface of described photoconductor 21.In described photoconductor 21, by this exposure, will utilize the surface charge of the part of light 29a irradiation to eliminate, make between the surface potential of the surface potential of the part of utilizing light 28a to irradiate and the part of not utilizing light 28a irradiation and there are differences, form thus electrostatic latent image.

Then, surface from from developing cell 25 to the described photoconductor 21 that has formed electrostatic latent image thereon provides toner with by latent electrostatic image developing, form thus toner image, wherein on the sense of rotation of photoconductor 21, the picture point of the light 28a launched with respect to exposure means 28, be arranged in downstream by described developing cell 25.

With the exposure of described photoconductor 21, synchronize, supply transfer paper 30 between described photoconductor 21 and described transfer printing unit 26.By described transfer printing unit 26, provide the electric charge with the opposite polarity of described toner for the transfer paper 30 of supplying, thereby will be transferred on described transfer paper 30 at the toner image formed on the surface of described photoconductor 21.

Then, by the transmission means by transfer printing on it transfer paper 30 of toner image be sent to fixation unit 31, during adjacency section between its warm-up mill by fixation unit 31 31a and backer roll 31b, heat and pressurize, with by toner image on transfer paper 30, form thus robust images (fast image).By the transmission means, the transfer paper 30 that has formed thus image on it is expelled to the outside of image processing system 20.

Simultaneously, even will after by transfer printing unit 26 transfer printing toner images, still remain in the lip-deep toner of photoconductor 21 by clearer 27, peel off and collect from the surface of photoconductor 21.By the light by except the electric light emission, the lip-deep electric charge of the photoconductor 21 of having removed in this way toner is eliminated, thereby make at the lip-deep electrostatic latent image of described photoconductor 21, disappear.Further drive described photoconductor 21 so that it rotate, and again repeat sequence of operations from charged beginning, thereby continuously form image thereafter.

Some pattern of described image processing system, can not have the cleaning means such as the clearer 27 that be used to removing and collecting, remain in the toner on photoconductor 21, and can not have to remain in surface charge on photoconductor 21 remove electricity except the electric hand section.

Hereinafter, will be with reference to the accompanying drawings, the undercoat in photoelectric conductor for electronic photography of the present invention is formed and is elaborated with the embodiment of coating fluid and manufacture method, photoelectric conductor for electronic photography and image processing system.Yet, the invention is not restricted to described embodiment.

Before for following embodiment, under normal pressure under 130 ℃ by whole heat dryings of surface-treated TiO 2 particles 1 hour.

Production Example 1

Manufacture TiOPc

At first, in nitrogen atmosphere, at the temperature of 200 ℃～250 ℃, α-chloronaphthalene of 40g phthalonitrile, 18g titanium tetrachloride and 500ml heated and stirred 3 hours, make reactant react and it is cooled to 100 ℃～130 ℃, then reaction product is carried out to heat filtering, utilization is heated to the 200ml α-chloronaphthalene of 100 ℃ and washs, thereby obtains the crude product of dichloro titanium-phthalocyanine.At room temperature, utilize α-chloronaphthalene of 200ml to wash crude product, then utilize 200ml methyl alcohol to wash, and in the methyl alcohol of 500ml, further carry out the thermal spray washing and continue 1 hour.After filtering, the crude product made is stirred and it is dissolved in the 100ml concentrated sulphuric acid, thereby insolubles is leached.Described sulfuric acid solution is added in 3000ml water, leaches and utilize the hot water of 500ml to repeat the thermal spray washing in the crystal made, until its pH reaches 6～7, and then filter.Utilize methylene chloride to process wet cake, utilize methyl alcohol to wash, then dry to obtain 32g TiOPc crystal, described crystal demonstrates the X-ray diffraction spectrum shown in Fig. 4 and has the structure meaned by following formula (I):

Obtained under the following conditions the X-ray diffraction spectrum of TiOPc crystal:

X-ray source

Voltage 30kV

Electric current 50mA

Start 5.0 °, angle

35.0 ° of angular stop

0.01 ° of stepping angle

1 °/minute of Measuring Time

Measuring method θ/2 θ scannings

X-ray diffraction spectrum shown in Fig. 4 shows, by the crystal-type TiOPc of the TiOPc obtained as mentioned above for locating to have the maximum diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 9.4 ° and locating to have diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 7.3 °, 9.7 ° and 27.3 ° at least, 9.4 ° and 9.7 ° of diffraction peaks of locating, be wherein bifurcated peak and compare large the diffraction peak of 27.3 ° clearly.

Production Example 2

Manufacture TiOPc

With with Production Example 1 in identical mode obtained the crude product of dichloro titanium-phthalocyanine, then at room temperature, utilize α-chloronaphthalene of 200ml to wash crude product, utilize 200ml methyl alcohol to wash, and in the methyl alcohol of 500ml, further carry out the thermal spray washing and continue 1 hour.After filtering, in the water of 500ml, the crude product made is repeated to the thermal spray washing, until its pH reaches 6～7, then carry out dry crystal-type TiOPc crystal (30g) to obtain the having structure meaned by formula (I) and to show the X-ray diffraction spectrum shown in Fig. 5.

As the situation in Production Example 1, the X-ray diffraction spectrum of crystal shown in Fig. 5 shows, by the crystal-type TiOPc of the TiOPc obtained as mentioned above for locating to have the maximum diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 27.3 ° and locating to have diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 7.4 °, 9.7 ° and 27.3 °.

Test I

Embodiment 1

Fig. 2 (b) is the schematic cross-sectional view that shows the embodiment of single layer type electrophotograph photoconductor of the present invention.

As shown in Fig. 2 (b), on conductive carrier 2, form undercoat 3, and on described undercoat 3, form the photographic layer 4 that contains charge generating material 8 and charge transport material 19.

Undercoat forms uses coating fluid

With up to half amount of container volume, using following ingredients with as the zirconia bead with 1mm diameter of dispersion medium, put into the polypropylene containers with 500ml volume, then utilize paint mixer to disperse with preparation 100g undercoat, to form and use coating fluid in 20 hours:

MAXLIGHT (registered trademark) TS-04 (is manufactured by Showa Denko K. K (Showa Denko K.K.), the titania that utilizes anhydride silica to process, titania: 67 % by weight, anhydride silica: 33 % by weight, the particle diameter of TiO 2 particles: 30nm, utilize the particle diameter of the TiO 2 particles that anhydride silica processed: 38nm) 0.76 weight portion

Titania MT-500SA (is manufactured the titania that utilizes aqueous silicon dioxide and aluminium hydroxide to process, titania: 90 % by weight, Al (OH) by Tayca ₃: 5 % by weight, SiO ₂NH ₂The O:5 % by weight) 0.19 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd. (Toray Industries, Inc.))

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

By using the baker coating device that undercoat is formed and is applied on the aluminium conductive carrier with 100 μ m thickness of conductive carrier 2 and under 110 ℃, utilizes heated-air drying 10 minutes with coating fluid, thereby form the undercoat 3 with 0.05 μ m build.

Photographic layer forms uses coating fluid

Then, on undercoat, utilize bowl mill to disperse following ingredients and continue 12 hours to prepare 50g photographic layer formation coating fluid:

TiOPc 17.1 weight portions that obtain in Production Example 1

Polycarbonate resin Z-400 (being manufactured by gas Co., Ltd. of Mitsubishi (Mitsubishi Gas Chemical Company, Inc.)) 17.1 weight portions

Hydrazone compound 17.1 weight portions of following formula (II)

Diphenoquinone compound 17.1 weight portions of following formula (III)

Tetrahydrofuran 100 weight portions.

Then with the baker coating device, be coated with coating fluid, under 100 ℃, utilize heated-air drying with formation, to have the photographic layer 4 of 20 μ m builds in 1 hour, thereby manufacture single layer type electrophotograph photoconductor 1b.

Embodiment 2

Except the undercoat for embodiment 1 forms with the titania in coating fluid and the content between resin, compare by following changing, manufactured single layer type electrophotograph photoconductor 1b in mode in the same manner as in Example 1.

MAXLIGHT (registered trademark) TS-04 (is manufactured by Showa Denko K. K, the titania that utilizes anhydride silica to process, titania: 67 % by weight, anhydride silica: 33 % by weight, the particle diameter of TiO 2 particles: 30nm, utilize the particle diameter of the TiO 2 particles that anhydride silica processed: 38nm) 0.08 weight portion

Titania MT-500SA (is manufactured the titania that utilizes aqueous silicon dioxide and aluminium hydroxide to process, titania: 90 % by weight, Al (OH) by Tayca ₃: 5 % by weight, SiO ₂NH ₂The O:5 % by weight) 0.02 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.9 weight portion

Embodiment 3

Fig. 2 (a) is the schematic cross-sectional view that shows the embodiment of function divergence type photoelectric conductor for electronic photography of the present invention.As shown in Fig. 2 (a), on conductive carrier 2, form undercoat 3, and on described undercoat 3 the stacking photographic layer 4 that comprises charge generation layer 5 and charge transport layer 6.In described structure, charge generation layer 5 comprises charge generating material 8 and charge transport layer 6 comprises charge transport material 18.

Undercoat forms uses coating fluid

With up to half amount of container volume, using following ingredients with as the zirconia bead with 1mm diameter of dispersion medium, put into the polypropylene containers with 500ml volume, then utilize paint mixer to disperse with preparation 100g undercoat, to form and use coating fluid in 20 hours:

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.76 weight portion

MT-500SA (being manufactured by Tayca) 0.19 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

By using the baker coating device that undercoat is formed and is applied on the aluminium conductive carrier with 100 μ m thickness of conductive carrier 2 and under 110 ℃, utilizes heated-air drying 10 minutes with coating fluid, thereby form the undercoat 3 with 5 μ m builds.

Then, utilize bowl mill to disperse following ingredients and continue 12 hours with preparation 50g charge generation layer formation coating fluid, then with the baker coating device, be coated with coating fluid, under 120 ℃, utilize heated-air drying with formation, to have the charge generation layer 5 of 0.8 μ m build in 10 minutes:

TiOPc 17.1 weight portions that obtain in Production Example 1

Vinyl chloride-vinyl acetate-maleic acid copolymerized resin SOLBINM (being manufactured by Nishin Chemical Industry Co. Lt (Nissin Chemical Industry Co., Ltd))

2 weight portions

Methyl ethyl ketone 100 weight portions

Charge transport layer forms uses coating fluid

In addition, following ingredients mixed, stirred and dissolve with preparation 100g charge transport layer formation coating fluid:

Hydrazone compound 8 weight portions of formula (II)

Polycarbonate resin K1300 (being manufactured by Teijin Chemicals, Ltd. (TEIJIN CHEMICALS LTD.)) 10 weight portions

Silicone oil KF50 (being manufactured by KCC of SHIN-ETSU HANTOTAI (Shin-Etsu Chemical Co., Ltd.)) 0.002 weight portion

Methylene chloride 120 weight portions 6

Use the baker coating device that coating fluid is applied on charge generation layer 5, under 80 ℃, utilize heated-air drying with formation, to have the charge transport layer 6 of 20 μ m builds in 1 hour, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 4

Except forming and be performed as follows change with the ratio of the content between the titania in coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.475 weight portion

MT-500SA (being manufactured by Tayca) 0.475 weight portion

Embodiment 5

Except forming and be performed as follows change with the ratio of the content between the titania in coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.285 weight portion

MT-500SA (being manufactured by Tayca) 0.665 weight portion

Embodiment 6

Except forming and be performed as follows change with the titania in coating fluid and the ratio of the content between resin for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.25 weight portion

MT-500SA (being manufactured by Tayca) 0.25 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.5 weight portion

Embodiment 7

Except forming and be performed as follows change with the titania in coating fluid for the undercoat of embodiment 6, in mode in the same manner as in Example 6, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-043 (is manufactured by Showa Denko K. K, the titania that utilizes anhydride silica to process, titania: 90 % by weight, anhydride silica: 10 % by weight, the particle diameter of titania: 30nm, utilize the particle diameter of the titania that anhydride silica processed: 32nm) 0.25 weight portion

MT-500SA (being manufactured by Tayca) 0.25 weight portion

Embodiment 8

Except forming and be performed as follows change with the titania in coating fluid for the undercoat of embodiment 6, in mode in the same manner as in Example 6, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-01 (is manufactured by Showa Denko K. K, the titania that utilizes anhydride silica to process, titania: 67 % by weight, anhydride silica: 33 % by weight, the particle diameter of TiO 2 particles: 90nm, utilize the particle diameter of the TiO 2 particles that anhydride silica processed: 110nm) 0.25 weight portion

MT-500SA (being manufactured by Tayca) 0.25 weight portion

Embodiment 9

Except forming, the charge generation layer for embodiment 7 changes into the TiOPc obtained in Production Example 2 with the TiOPc that will obtain in Production Example 1 in coating fluid, in mode in the same manner as in Example 7, prepared undercoat and photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 10

Except forming, the charge generation layer for embodiment 7 changes into τ type metal-free phthalocyanine Liophoton TPA-891 (by (the Toyo Ink Mfg.Co. of Toyo Ink Co., Ltd. with the TiOPc that will obtain in coating fluid in Production Example 1, Ltd.) manufacture) outside, in mode in the same manner as in Example 7, prepared undercoat and photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 11

Except forming and be performed as follows change with the titania in coating fluid and the ratio of the content between resin for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.64 weight portion

MT-500SA (being manufactured by Tayca) 0.16 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.2 weight portion

Embodiment 12

Except forming, the charge generation layer for embodiment 11 changes into the TiOPc obtained in Production Example 2 with the TiOPc that will obtain in Production Example 1 in coating fluid, with with embodiment 11 in identical mode prepared undercoat and photographic layer, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 13

Except forming and be performed as follows change with the titania in coating fluid for the undercoat of embodiment 11, with embodiment 11 in identical mode prepared photographic layer, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.24 weight portion

MT-500SA (being manufactured by Tayca) 0.56 weight portion

Embodiment 14

Except forming, the charge generation layer for embodiment 13 changes into the TiOPc obtained in Production Example 2 with the TiOPc that will obtain in Production Example 1 in coating fluid, with with embodiment 13 in identical mode prepared undercoat and photographic layer, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 1

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MT-500SA (being manufactured by Tayca) 0.95 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Comparative example 2

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MAXLIGHT (registered trademark) TS-04 (being manufactured by Showa Denko K. K)

0.95 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Comparative example 3

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

0.95 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Comparative example 4

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MAXLIGHT (registered trademark) TS-01 (being manufactured by Showa Denko K. K)

0.95 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Comparative example 5

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

0.855 weight portion

MT-500SA (being manufactured by Tayca) 0.095 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Comparative example 6

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 3, in mode in the same manner as in Example 3, prepared undercoat, then in mode in the same manner as in Example 3, prepared photographic layer, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

0.19 weight portion

MT-500SA (being manufactured by Tayca) 0.76 weight portion

Polyamide (CM8000 is manufactured by Dongli Ltd.)

0.05 weight portion

Methyl alcohol 50 weight portions

1,3-dioxane, 50 weight portions.

Embodiment 15

In mode in the same manner as in Example 1, form undercoat, then, in mode in the same manner as in Example 1, form the photographic layer 4 with 16 μ m builds, thereby manufacture single layer type electrophotograph photoconductor 1b.

Embodiment 16

In mode in the same manner as in Example 2, form undercoat, then, in mode in the same manner as in Example 2, form the photographic layer 4 with 16 μ m builds, thereby manufacture single layer type electrophotograph photoconductor 1b.

Embodiment 17

In mode in the same manner as in Example 3, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 3, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 18

In mode in the same manner as in Example 4, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 4, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 19

In mode in the same manner as in Example 5, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 5, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 20

In mode in the same manner as in Example 6, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 6, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 21

In mode in the same manner as in Example 7, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 7, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 22

In mode in the same manner as in Example 8, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 8, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 23

In mode in the same manner as in Example 9, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 9, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 24

In mode in the same manner as in Example 10, form undercoat, then, form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon in mode in the same manner as in Example 10, thus manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 25

With with embodiment 11 in identical mode form undercoat, then, with embodiment 11 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 26

With with embodiment 12 in identical mode form undercoat, then, with embodiment 12 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 27

With with embodiment 13 in identical mode form undercoat, then, with embodiment 13 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Embodiment 28

With with embodiment 14 in identical mode form undercoat, then, with embodiment 14 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 7

With with comparative example 1 in identical mode form undercoat, then, with comparative example 1 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 8

With with comparative example 2 in identical mode form undercoat, then, with comparative example 2 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 9

With with comparative example 3 in identical mode form undercoat, then, with comparative example 3 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 10

With with comparative example 4 in identical mode form undercoat, then, with comparative example 4 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 11

With with comparative example 5 in identical mode form undercoat, then, with comparative example 5 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Comparative example 12

With with comparative example 6 in identical mode form undercoat, then, with comparative example 6 in identical mode form charge generation layer and form the charge transport layer 6 with 16 μ m builds thereon, thereby manufacturing function divergence type photoelectric conductor for electronic photography 1a.

Undercoat by using preparation in embodiment 1～28 and comparative example 1～12 as mentioned above and photoconductor that photographic layer is manufactured are placed on respectively by digital copier (AR-451M, by Sharp Corporation (Sharp Kabushiki kaisha), manufactured) transform and around the aluminium drum of the machine that obtains, and print white solid image by reversal development, thereby estimate respectively according to following evaluation method.

Estimate white solid image

With the digital copier that is equipped with the various photoconductors of manufacturing in embodiment 1～28 and comparative example 1～12, print white solid image, thereby estimate the solid image of initial white under high temperature/high humidity environment (35 ℃/85%) according to following evaluation criterion.Under 850 grid bias, estimate initial white solid image, keep simultaneously the poor of grid bias and DV bias voltage constant, described 850 grid bias are higher by 200 than normal use value.

VG (very good): do not observe black spot defect.

G (well): observe some black spot defect.

B (poor): observe many black spot defect.

VB (non-constant): observe the image atomization.

Following table has shown evaluation result.

Table 1

Example	Initial white solid image	Example	Initial white solid image
				Embodiment 1	G	Embodiment 15	G
Embodiment 2	G	Embodiment 16	G
				Embodiment 3	VG	Embodiment 17	VG
Embodiment
	4	VG	Embodiment	18	VG
Embodiment 5						VG	Embodiment	19	VG
	Embodiment 6	VG	Embodiment	20	VG
Embodiment
	7	VG	Embodiment	21	VG
Embodiment
	8	VG	Embodiment	22	VG
Embodiment
	9	VG	Embodiment	23	VG
Embodiment
	10	VG	Embodiment	24	VG
Embodiment
	11	VG	Embodiment	25	VG
Embodiment
	12	VG	Embodiment	26	VG
Embodiment
	13	VG	Embodiment	27	VG
Embodiment
	14	VG	Embodiment	28	VG
Comparative example 1						VG	Comparative example 7	VB
	Comparative example 2	VG	Comparative example 8	B
Comparative example 3					VG	Comparative example 9	B
	Comparative example 4	VG	Comparative example 10	B
Comparative example 5					VG	Comparative example 11	B
	Comparative example 6	VG	Comparative example 12	VB

The evaluation result of initial white solid image shows, in the printed article that the digital copier of gained photoconductor in being equipped with embodiment 1～28 is manufactured, do not observe defect or observe some insignificant defects and obtained not the good image that can throw into question to normal use.On the other hand, at photoconductor, have in the situation of the larger film thickness degree in comparative example 1～6, obtain good image, but in the printed article that the photoconductor of less film thickness is manufactured in having comparative example 7～12 by use, observed image atomization and many black spot defect (photoconductor with limiting film thickness degree: even the film thickness when when the voltage on being applied to charged device changed, the surface potential on photoconductor no longer linear change occurred).

When under the digital copier for estimating and the normal grid bias at charged device, the film thickness of the photoconductor in embodiment 15～28 and comparative example 7～12 shown with embodiment 1～14 and comparative example 1～6 in the comparable charging property of photoconductor.

The evaluation of dispersion stabilization

In addition, the undercoat obtained is formed with standing one month of coating fluid and six months to check whether there is condensation product, using evaluation as dispersion stabilization.

G (well): do not observe condensation product.

NB (not poor): observe some condensation products, but can use in normal running.

B (poor): observe the sedimentation of condensation product, unavailable.

Following table has shown evaluation result.

Table 2

Example	One month	Six months
			Embodiment 1	G	NB
Embodiment 2	G	NB
			Embodiment 3	G	NB
Embodiment 4	G	NB
			Embodiment 5	G	NB
Embodiment 6	G	G
			Embodiment 7	G	G
Embodiment 8	G	G
			Embodiment 9	G	G
Embodiment 10	G	G
			Embodiment 11	G	G
Embodiment 12	G	G
			Embodiment 13	G	G
Embodiment 14	G	G

Comparative example 1	G	B
			Comparative example 2	G	B
Comparative example 3	G	B
			Comparative example 4	G	B
Comparative example 5	G	B
			Comparative example 6	G	B

Undercoat is formed and compares with the dispersion stabilization between coating fluid.In embodiment 1～14 and comparative example 1～6, after one month, do not observe condensation product.Yet, in embodiment 1～5, after six months, observe some condensation products, this uses and can not throw into question reality.In comparative example 1～6, observe the more condensation product than embodiment 1～5, thereby it is poor to show that undercoat forms with the dispersion stabilization of coating fluid.

Embodiment 29

With the amount up to bead mill volume 80%, silicon nitride as the dispersion medium globule that will have the 0.5mm diameter is put into the horizontal bead mill with 16500mL volume, then, following ingredients is stored in tank diameter and is sent in dispersion machine under circulation, to disperse and to continue 15 hours by membrane pump, thus preparation 3000g undercoat formation coating fluid:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

4 weight portions

MT-500SA (being manufactured by Tayca) 4 weight portions

Polyamide (X1010 is manufactured by Daicel-Degussa Co., Ltd. (Daicel-Degussa Ltd.)) 2 weight portions

Ethanol 50 weight portions

Tetrahydrofuran 50 weight portions.

The coating container of this coating fluid is equipped with in utilization, by dip coating as conductive carrier and have the 30mm diameter and the cylindric alumina supporter of 345mm total length on form the undercoat with 0.05 μ m film thickness.

Then, utilize bowl mill to disperse the potpourri of following ingredients and continue 12 hours with preparation 2000g charge generation layer formation coating fluid,

TiOPc 2 weight portions that obtain in Production Example 1

Polyvinyl butyral resin (S-LEC BM-S is manufactured by Sekisui Fine Chemical Co., Ltd. (SEKISUI CHEMICAL Co., Ltd)) 2 weight portions

Methyl ethyl ketone 100 weight portions.

Then, be applied to this coating fluid on undercoat and under 120 ℃, utilize heated-air drying 10 minutes by method identical in the situation with undercoat, thereby forming the charge generation layer 5 with 0.8 μ m build.

Subsequently, following ingredients mixed and dissolve with preparation 3000g charge transport layer formation coating fluid:

Enamine compound 10 weight portions by formula (IV) expression

Polycarbonate resin (Z200 is manufactured by Mitsubishi engineering Plastics Co., Ltd (Mitsubishi Engineering-Plastics Corporation)) 10 weight portions

Silicone oil KF50 (being manufactured by KCC of SHIN-ETSU HANTOTAI) 0.02 weight portion

Tetrahydrofuran 120 weight portions

Then, by method identical in the situation with undercoat, be applied to coating fluid on charge generation layer and the dry charge transport layer that had 23 μ m film thicknesses in 1 hour with formation under 110 ℃.

Thus, manufactured the function divergence type photoelectric conductor for electronic photography as sample.

Embodiment 30

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 29, with embodiment 29 in identical mode prepared 3000g undercoat formation coating fluid:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

4 weight portions

MT-500SA (being manufactured by Tayca) 4 weight portions

Polyamide (M1276 is manufactured by Arkema (Arkema))

2 weight portions

Methyl alcohol 50 weight portions

Tetrahydrofuran 50 weight portions.

The coating container of this coating fluid is equipped with in utilization, by dip coating as conductive carrier and have the 30mm diameter and the cylindric alumina supporter of 345mm total length on form the undercoat with 1.0 μ m film thicknesses.

Then, with embodiment 29 in identical mode formed successively charge generation layer and charge transport layer, thereby produce the function divergence type photoelectric conductor for electronic photography as sample.

Comparative example 13

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 29, with embodiment 29 in identical mode prepared 3000g undercoat formation coating fluid:

MAXLIGHT (registered trademark) TS-043 (being manufactured by Showa Denko K. K)

8 weight portions

Polyamide (M1276 is manufactured by A Kema) 2 weight portions

Methyl alcohol 50 weight portions

Tetrahydrofuran 50 weight portions.

With with embodiment 29 in identical mode, utilize undercoat to form and formed undercoat with coating fluid, then formed successively charge generation layer and charge transport layer, thereby produced the function divergence type photoelectric conductor for electronic photography as sample.

Comparative example 14

Except forming and change into following ingredients with the composition of coating fluid for the undercoat of embodiment 29, with embodiment 29 in identical mode prepared 3000g undercoat formation coating fluid:

MT-500SA (being manufactured by Tayca) 8 weight portions

Polyamide (M1276 is manufactured by A Kema) 2 weight portions

Methyl alcohol 50 weight portions

Tetrahydrofuran 50 weight portions.

With with embodiment 29 in identical mode, utilize undercoat to form and formed undercoat with coating fluid, then formed successively charge generation layer and charge transport layer, thereby produced the function divergence type photoelectric conductor for electronic photography as sample.

To be arranged in digital copier (AR-451M is manufactured by Sharp) and measure the initial strip electric potential V under normal temperature/normal humidity (N/N, 22 ℃/65%) environment by the photoelectric conductor for electronic photography as sample of manufacturing as mentioned above ₀, initial bright current potential (bright potential) V after laser explosure _L, initial bright current potential V under low temperature/low humidity (L/L, 5 ℃/10%) environment _L, and initial bright current potential V under high temperature/high humidity (H/H, 35 ℃/85%) environment _LUsing test as electrical characteristics stability.

Herein, V ₀Refer to when not carrying out laser explosure the directly surface potential of the photoconductor after carrying out hot line job by charged device, and V _LRefer to the directly surface potential of the photoconductor after laser explosure.

In addition, to the starting stage with by reality, duplicate 50000 (50k opens) and 100000 (100k opens) and carry out picture characteristics after aging and carried out check and using as endurancing.

VG (very good): do not observe black spot defect.

G (well): observe some black spot defect.

B (poor): observe many black spot defect.

VB (non-constant): observe the image atomization.

Following table has shown result.

Table 3

Table 4

Table 5

In upper table, embodiment 29 and 30 result show, current potential is highly stable, and this demonstrates not only under N/N (normal temperature/normal humidity) environment but also follows V under Condition of Environment Changes _LAll be difficult to change.

, in picture appraisal, do not observe atomization or black spot defect herein, thereby confirmed the image quality excellence.

On the other hand, in comparative example 14, under the L/L environment since starting stage current potential V _LPoor and produce atomization with regard to height and susceptibility.

In by long-term reality, duplicating carry out aging, observed black spot defect herein.In comparative example 13, obtained better picture characteristics, but the actual duplicating by very long-time carry out aging in observed black spot defect.

That is, show, the photoconductor obtained in comparative example 13 and 14 is not suitable for actual use because when environmental change V _LRaise, and using image deterioration when reaching duplicating 100k and opening because of long-term.

Industrial applicibility

Even the present invention can provide a kind of, when long-term the use, still have high sensitive and under all environment from the low temperature and low humidity environment to hot and humid environment, all have the photoconductor of excellent electrical characteristic and show by the photographic layer that use has a following undercoat image processing system that there is no the excellent image of image deflects characteristic, described undercoat contains adhesive resin and utilizes the surface-treated TiO 2 particles of anhydride silica and utilize surface-treated two kinds of particles of TiO 2 particles of aqueous silicon dioxide at least.

Claims (13)

1. photoelectric conductor for electronic photography, it comprises conductive carrier, undercoat and photographic layer, and described undercoat and photographic layer are formed on described conductive carrier successively,

Wherein said undercoat contains:

Adhesive resin,

Utilize the surface-treated TiO 2 particles of anhydride silica, and

The TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process,

Wherein with 80/20～30/70 weight ratio, comprise the described TiO 2 particles that utilizes the surface-treated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and surface of aluminum hydroxide to process, and

Wherein with respect to the titania used, the anhydride silica of cladding titanium dioxide particle surface, aqueous silicon dioxide and aluminium hydroxide are 0.1 % by weight～50 % by weight for the surface-treated use amount separately.

2. photoconductor as claimed in claim 1, the wherein said TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process are to utilize the aqueous silicon dioxide that mixes with 10/90～90/10 weight ratio and the surface-treated TiO 2 particles of potpourri of aluminium hydroxide.

3. photoconductor as claimed in claim 1, wherein said photographic layer contains phthalocyanine as charge generating material.

4. photoconductor as claimed in claim 1, wherein said photographic layer contain and are selected from following phthalocyanine as charge generating material: τ type metal-free phthalocyanine; In X-ray diffraction spectrum, locate to have the crystal-type TiOPc at maximum diffraction peak at the Bragg angle (2 θ ± 0.2 °) of 27.3 °; At least the Bragg angle (2 θ ± 0.2 °) 7.3 °, 9.4 °, 9.7 ° and 27.3 ° locates to have diffraction peak in X-ray diffraction spectrum, wherein at 9.4 ° and 9.7 ° of diffraction peaks of locating bifurcated peak and than large 27.3 ° of diffraction peaks of locating clearly both, and at 9.4 ° of diffraction peaks of locating crystal-type TiOPc that is maximum diffraction peaks.

5. photoconductor as claimed in claim 1, wherein said TiO 2 particles has the average primary particle diameter of 20nm～100nm.

6. photoconductor as claimed in claim 1, with respect to the described adhesive resin weight ratio as 10/90～95/5 of wherein take in described undercoat comprise and describedly utilize the surface-treated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and TiO 2 particles that surface of aluminum hydroxide was processed.

7. photoconductor as claimed in claim 1, wherein said adhesive resin is polyamide.

8. photoconductor as claimed in claim 1, wherein said undercoat has the film thickness of 0.05 μ m～5 μ m.

9. photoconductor as claimed in claim 1, wherein said photographic layer is the multilayer photographic layer that comprises charge generation layer and charge transport layer, described charge generation layer has the film thickness of 0.05 μ m～5 μ m.

10. image processing system, it comprises photoelectric conductor for electronic photography claimed in claim 1.

11. an image forming method, it comprises that right to use requires 10 described image processing systems.

12. the undercoat for the manufacture of photoelectric conductor for electronic photography forms, use coating fluid, described photoelectric conductor for electronic photography comprises conductive carrier, undercoat and photographic layer, and described undercoat and photographic layer are formed on described conductive carrier successively,

Described coating fluid contains:

Adhesive resin,

Utilize the surface-treated TiO 2 particles of anhydride silica, and

The TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process,

Wherein with 80/20～30/70 weight ratio, comprise the described TiO 2 particles that utilizes the surface-treated TiO 2 particles of anhydride silica and utilize aqueous silicon dioxide and surface of aluminum hydroxide to process, and

Wherein with respect to the titania used, the anhydride silica of cladding titanium dioxide particle surface, aqueous silicon dioxide and aluminium hydroxide are 0.1 % by weight～50 % by weight for the surface-treated use amount separately.

13. coating fluid as claimed in claim 12, the wherein said TiO 2 particles that utilizes aqueous silicon dioxide and surface of aluminum hydroxide to process are to utilize the aqueous silicon dioxide that mixes with 10/90～90/10 weight ratio and the surface-treated TiO 2 particles of potpourri of aluminium hydroxide.

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